Quaternized tetrazine-based donor-acceptor copolymers

ABSTRACT

A quaternized tetrazine-based donor-acceptor (D-A) copolymer is disclosed.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional application of and claims priority fromU.S. patent application Ser. No. 16/014,720, filed Jun. 21, 2018, whichis a divisional of U.S. patent application Ser. No. 15/226,961, now U.S.Pat. No. 10,056,553, filed Aug. 3, 2016.

BACKGROUND

Renewable energy and materials is a rapidly growing field, thedevelopment of which is in higher demand than ever. One major branch ofrenewable energy is organic electronics and semiconducting materials.Organic semiconductors have several advantages over their silicon-basedcounterparts including renewability, their ability to besolution-processed into lightweight and flexible films, and theirability to have their properties easily tuned through chemicalsynthesis.

Important progress has been made towards making organic semiconductortechnology ubiquitous in everyday uses. Technologies such as organicphotovoltaics (OPVs) and organic batteries may provide a practical pathto achieve low-cost, renewable energy harvesting, and storage. Plasticpolymeric power generation and storage sources offer intriguingopportunities for both portable solar cells and batteries, as suchmaterials are potentially flexible, lightweight, and easy to fabricatethrough low-cost processing techniques. Further, organic molecules mayoffer malleable properties that are easy to tune through chemicalsynthesis.

Typically, organic semiconducting materials (OSMs) are only soluble inorganic solvents, and sometimes this solubility may be limited. This lowsolubility is mostly due to OSM designs having a highly planar naturethat allows for optimal overlap of their pi-electron clouds and a highdegree of crystallinity. The problem of solubility is typically dealtwith by affixing alkyl side chains to the aromatic molecules that makeup the polymer (or small molecule) backbone. Finding the appropriateside chain is unique to each new donor-acceptor polymer system that isdesigned, and certain chains lengths and chain branching works betterfor some systems than others. This delicate balance between solubilityand planarity can make for long and arduous molecular designing toobtain the ideal material.

The vast majority of polymers that have been successfully used in OPVsare comprised of an alternating electron-rich (donor) andelectron-deficient (acceptor) co-monomers, called donor-acceptor (D-A)copolymers. Typically, it is much easier, for synthetic reasons, toaffix alkyl chains to the donor molecules. For this reason, the libraryof known donor molecules is much more diverse than that of the acceptormolecules. There exists a need for acceptors that can also positivelyaffect solubility.

SUMMARY

According to an embodiment, a quaternized tetrazine-based donor-acceptor(D-A) copolymer is disclosed.

According to another embodiment, an organic photovoltaic device isdisclosed. The organic photovoltaic device comprises an active layerthat includes a quaternized tetrazine-based donor-acceptor (D-A)copolymer.

According to another embodiment, a process of forming a quaternizedtetrazine-based donor-acceptor (D-A) copolymer is disclosed. The processincludes forming a quaternized tetrazine monomer and polymerizing thequaternized tetrazine monomer and a donor molecule to form thequaternized tetrazine-based D-A copolymer.

The foregoing and other objects, features and advantages of theinvention will be apparent from the following more particulardescriptions of exemplary embodiments of the invention as illustrated inthe accompanying drawings wherein like reference numbers generallyrepresent like parts of exemplary embodiments of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a chemical reaction diagram illustrating the formation of aquaternized tetrazine monomer, according to one embodiment.

FIG. 1B is a chemical reaction diagram illustrating the formation of aquaternized tetrazine monomer, according to one embodiment.

FIG. 2 is a chemical reaction diagram illustrating the formation of aquaternized tetrazine-based donor-acceptor (D-A) copolymer, according toone embodiment.

FIG. 3 is a chemical reaction diagram illustrating the formation of aquaternized tetrazine-based donor-acceptor (D-A) copolymer, according toone embodiment.

FIGS. 4A and 4B are chemical reaction diagrams illustrating theformation of a quaternized tetrazine-based donor-acceptor (D-A)copolymer, according to one embodiment.

FIGS. 5A and 5B are chemical reaction diagrams illustrating theformation of a quaternized tetrazine-based donor-acceptor (D-A)copolymer, according to one embodiment.

FIGS. 6A and 6B are chemical reaction diagrams illustrating theformation of the tetrazine monomer precursor depicted in FIGS. 1A and1B, according to one embodiment.

FIG. 7 is a chemical reaction diagram illustrating the formation of thetetrazine monomer precursor depicted in FIGS. 1A and 1B, according toone embodiment.

FIG. 8 is a chemical reaction diagram illustrating the formation of thetetrazine monomer precursor depicted in FIGS. 1A and 1B, according toone embodiment.

FIG. 9 is a flow diagram showing a particular embodiment of a process offorming a quaternized tetrazine-based donor-acceptor (D-A) copolymer.

FIG. 10 is a flow diagram showing a particular embodiment of a processof forming an active layer of an organic photovoltaic (OPV) device thatincludes a quaternized tetrazine-based donor-acceptor (D-A) copolymer.

DETAILED DESCRIPTION

The present disclosure describes quaternized tetrazine-baseddonor-acceptor (D-A) copolymers and methods of forming the quaternizedtetrazine-based D-A copolymers. In the present disclosure, theincorporation of an acceptor molecule may provide the ability to impartnot only good solubility, but also solubility in a broad array ofsolvents. Such solvents may include typical options such as chloroform,chlorobenzenes, dimethylformamide (DMF), toluene, and tetrahydrofuran(THF), but may also include polar protic solvents such as water,ethanol, and isopropanol. Such solubility characteristics may beimparted by using an electron deficient, anionic moiety, wherebyswitching the counter cations may enable alteration of a solubilityprofile.

In some cases, as described further herein, the quaternizedtetrazine-based D-A copolymers of the present disclosure may be utilizedto fabricate an OPV device. The OPV device fabrication may be done asblends with organic molecules as is typical for OPV devices, or withinorganic molecules such as perovskites (which is atypical for OPVdevices), by taking advantage of the variable solubility profileafforded to the polymer by the nature of the counter cations. Thepotential for solubility in polar protic solvents also allows these D-Acopolymers to be fabricated orthogonally with other organic layers. Thisorthogonal processability represents another advantage associated withthe quaternized tetrazine-based D-A copolymers of the presentdisclosure.

Referring to FIGS. 1A and 1B, a diagram 100 depicts illustrativeexamples of processes of forming quaternized tetrazine monomers for usein forming the quaternized tetrazine-based D-A copolymers of the presentdisclosure. In FIG. 1A, a tetrazine monomer precursor is utilized toform a first quaternized tetrazine monomer (identified as “QuaternizedTetrazine Monomer(1)” in FIG. 1A). In FIG. 1B, the tetrazine monomerprecursor is utilized to form a second quaternized tetrazine monomer(identified as “Quaternized Tetrazine Monomer(2)” in FIG. 1B). In somecases, the tetrazine monomer precursor depicted in FIGS. 1A and 1B maybe formed according to the example processes described further hereinwith respect to FIGS. 6A-6B, FIG. 7, and FIG. 8.

FIGS. 1A and 1B illustrate that the tetrazine monomer precursor may bereacted with either thionyl chloride or an alkylsulfonyl fluoride (wherethe alkyl chains can be selected from C4-C20 in length, linear orbranched) via simultaneous nucleophilic substitution conditions of thetetrazine imines at the carbons bonded to the TBS-protected hydroxylgroups. The result is a tetra-quaternized tetrazinium monomer. Selectingthe reagents and conditions of the nucleophilic substitutions results indifferent counter cations which affect the solubility of the monomer andany resulting polymers synthesized from the monomers. Using thionylchloride (as depicted in FIG. 1A) results in a water soluble polymer(among other solvents). Using the alkylsulfonyl fluoride chemical (asdepicted in FIG. 1B) results in four counter cations with alkyl sulfideswhere the alkyl chains of the monomer can be selected to promotesolubility in common organic solvents.

In FIG. 1A, the first quaternized tetrazine monomer is synthesized usingthionyl chloride to give a tetra-chloride version of a quaternizedtetrazine monomer for subsequent polymerization with a donor molecule toform a quaternized tetrazine-based D-A copolymer (as depicted in FIG.2). In FIG. 1B, the second quaternized tetrazine monomer is synthesizedvia TBAF and an alkylsulfate fluoride compound (depicted as “RSO₂F” inFIG. 1B) to form an alkylate sulfite version of a quaternized tetrazinemonomer for subsequent polymerization with a donor molecule to form aquaternized tetrazine-based D-A copolymer (as depicted in FIG. 3).

PROPHETIC EXAMPLE Formation of Quaternized Tetrazine Monomer(1)

To a solution of the tetrazine in an organic solvent which may includeacetonitrile, chloroform, chlorobenzene, etc. may be added thionylchloride, and the reaction mixture may be stirred at room temperaturefor 24 hours. The solvents may be removed in vacuo, and the resultingsolid residue may be washed with solvents which may include methanol andDMF. The crude solid may be recrystallized from a mixture of solventsthat may include water, methanol, ethanol, and/or acetone.

Prophetic Example Formation of Quaternized Tetrazine Monomer(2)

To a solution of the tetrazine in an organic solvent which may includeacetonitrile, chloroform, chlorobenzene, etc. may be added analkylsulfite fluoride and a 1 M solution of TBAF in THF, and thereaction mixture may be stirred at reflux for 24 hours. The reaction maybe cooled to room temperature and may be precipitated into hexane, andfiltered. The crude solid may be recrystallized from a mixture ofsolvents that may include methanol, ethanol, and/or acetone, hexane,dichloromethane, chloroform.

Thus, FIGS. 1A and 1B depict examples of processes of formingquaternized tetrazine monomers. As described further herein with respectto FIG. 2, FIG. 3, FIGS. 4A and 4B, and FIGS. 5A and 5B, the quaternizedtetrazine monomers depicted in FIGS. 1A and 1B may be utilized to formquaternized tetrazine-based D-A copolymers. In some cases, thequaternized tetrazine-based D-A copolymers formed from the quaternizedtetrazine monomers depicted in FIGS. 1A and 1B may be fabricated intoOPV devices.

Referring to FIG. 2, a chemical reaction diagram 200 depicts an exampleof a process of utilizing the first quaternized tetrazine monomerdepicted in FIG. 1A to form a first quaternized tetrazine-based D-Acopolymer (identified as “Quaternized Tetrazine-Based D-A Copolymer(1)”in FIG. 2).

FIG. 2 illustrates that the first quaternized tetrazine monomer of FIG.1A may be polymerized with donor (electron rich) molecules bycross-coupling conditions. FIG. 2 depicts a non-limiting, illustrativeexample in which the donor (electron rich) molecule is alkoxy-BDTbistrimethylstannane. In other embodiments, alternative and/oradditional donor molecules may be utilized.

PROPHETIC EXAMPLE Formation of Quaternized Tetrazine-Based D-ACopolymer(1)

An oven-dried, Schlenk flask may be charged with dry, deoxygenatedtoluene (5-10 mL), dibromobisphenyltetrazine monomer (1.0 equiv.), and abisstannane-functionalized donor monomer (1.05 equiv.). The stirredsolution may be sparged with argon for 10 minutes and may be followed bythe addition of tris(dibenzylideneacetone)dipalladium(0) (2 mol %) andtri(o-tolyl)phosphine (8 mol %). The reaction mixture may be heated toreflux and stirred, under argon, for 4-96 hours. The polymer may beend-capped by the subsequent addition of an excess amount oftrimethyl(phenyl)tin and iodobenzene, each may be followed by up to a 4hour period of reflux. The reaction mixture may be cooled to 50° C. andmay be diluted with chloroform. A small portion of SiliaMetS® Cysteinemay be added and the reaction mixture and may be followed by beingstirred for 8 hours. The polymer may be precipitated into a cold,organic non-solvent such as methanol, acetone, or hexane and may befiltered. The polymer may be purified by any combination of Soxhletextraction, reprecipitation, filtration, column chromatography, or othertechniques.

Thus, FIG. 2 illustrates an example of a process of utilizing aquaternized tetrazine monomer to form a quaternized tetrazine-based D-Acopolymer. As described further herein, the quaternized tetrazine-basedD-A copolymer of FIG. 2 may be utilized to fabricate an OPV device. TheOPV device fabrication may be done as blends with organic molecules asis typical for OPV devices, or with inorganic molecules such asperovskites (which is atypical for OPV devices), by taking advantage ofthe variable solubility profile afforded to the polymer by the nature ofthe counter cations. The potential for solubility in polar proticsolvents also allows these D-A copolymers to be fabricated orthogonallywith other organic layers. This orthogonal processability representsanother advantage associated with the quaternized tetrazine-based D-Acopolymers of the present disclosure.

Referring to FIG. 3, a chemical reaction diagram 300 depicts an exampleof a process of utilizing the second quaternized tetrazine monomerdepicted in FIG. 1B to form a second quaternized tetrazine-based D-Acopolymer (identified as “Quaternized Tetrazine-Based D-A Copolymer(2)”in FIG. 3).

FIG. 3 illustrates that the second quaternized tetrazine monomer of FIG.1B may be polymerized with donor (electron rich) molecules bycross-coupling conditions. FIG. 3 depicts a non-limiting, illustrativeexample in which the donor (electron rich) molecule is alkoxy-BDTbistrimethylstannane. In other embodiments, alternative and/oradditional donor molecules may be utilized.

PROPHETIC EXAMPLE Formation of Quaternized Tetrazine-based D-ACopolymer(2)

An oven-dried, Schlenk flask may be charged with dry, deoxygenatedtoluene (5-10 mL), dibromobisphenyltetrazine monomer (1.0 equiv.), and abisstannane-functionalized donor monomer (1.05 equiv.). The stirredsolution may be sparged with argon for 10 minutes and may be followed bythe addition of tris(dibenzylideneacetone)dipalladium(0) (2 mol %) andtri(o-tolyl)phosphine (8 mol %). The reaction mixture may be heated toreflux and stirred, under argon, for 4-96 hours. The polymer may beend-capped by the subsequent addition of an excess amount oftrimethyl(phenyl)tin and iodobenzene, each may be followed by up to a 4hour period of reflux. The reaction mixture may be cooled to 50° C. andmay be diluted with chloroform. A small portion of SiliaMetS® Cysteinemay be added and the reaction mixture and may be followed by beingstirred for 8 hours. The polymer may be precipitated into a cold,organic non-solvent such as methanol, acetone, or hexane and may befiltered. The polymer may be purified by any combination of Soxhletextraction, reprecipitation, filtration, column chromatography, or othertechniques.

Thus, FIG. 3 illustrates an example of a process of utilizing aquaternized tetrazine monomer to form a quaternized tetrazine-based D-Acopolymer. As described further herein, the quaternized tetrazine-basedD-A copolymer of FIG. 3 may be utilized to fabricate an OPV device. TheOPV device fabrication may be done as blends with organic molecules asis typical for OPV devices, or with inorganic molecules such asperovskites (which is atypical for OPV devices), by taking advantage ofthe variable solubility profile afforded to the polymer by the nature ofthe counter cations. The potential for solubility in polar proticsolvents also allows these D-A copolymers to be fabricated orthogonallywith other organic layers. This orthogonal processability representsanother advantage associated with the quaternized tetrazine-based D-Acopolymers of the present disclosure.

FIGS. 4A, 4B, 5A, and 5B depict alternative synthesis schemes in whichthe quaternized tetrazine-based D-A copolymers may be synthesized byfirst polymerizing the TBS-protected molecule with donor molecule(s) andthen subjecting the resulting tetrazine-based copolymer to apost-polymerization quaternization of the tetrazine imines.

Referring to FIGS. 4A and 4B, a diagram 400 depicts an example of analternative sequence of chemical reactions to form the first quaternizedtetrazine-based D-A copolymer depicted in FIG. 2. FIG. 4A is a firstchemical reaction diagram that illustrates an example process of forminga tetrazine-based copolymer, and FIG. 4B is a second chemical reactiondiagram that illustrates an example of a process of utilizing thetetrazine-based copolymer to form the first quaternized tetrazine-basedD-A copolymer.

With respect to the chemical reaction depicted in FIG. 4A, similarreaction conditions to those described above with respect to FIGS. 2 and3 may be utilized to form the tetrazine-based copolymer from theTBS-protected molecule and the donor molecule. With respect to thechemical reaction depicted in FIG. 4B, similar reaction conditions tothose described above with respect to FIG. 1A may be utilized to formthe first quaternized tetrazine-based D-A copolymer.

Referring to FIGS. 5A and 5B, a diagram 500 depicts an example of analternative sequence of chemical reactions to form the secondquaternized tetrazine-based D-A copolymer depicted in FIG. 3. FIG. 5A isa first chemical reaction diagram that illustrates an example process offorming a tetrazine-based copolymer, and FIG. 5B is a second chemicalreaction diagram that illustrates an example of a process of utilizingthe tetrazine-based copolymer to form the second quaternizedtetrazine-based D-A copolymer.

With respect to the chemical reaction depicted in FIG. 5A, similarreaction conditions to those described above with respect to FIGS. 2 and3 may be utilized to form the tetrazine-based copolymer from theTBS-protected molecule and the donor molecule. With respect to thechemical reaction depicted in FIG. 5B, similar reaction conditions tothose described above with respect to FIG. 1B may be utilized to formthe second quaternized tetrazine-based D-A copolymer.

FIGS. 6A, 6B, 7, and 8 illustrate alternative example of processes forforming the tetrazine monomer precursor material depicted in FIGS. 1Aand 1B. As described further herein, the proposed tetrazine-basedmonomers may be synthesized via alternative synthetic pathways startingfrom commercially available 5-bromo-2-iodo-1,3-dimethylbenzene. Thetetrazine monomer precursors may be synthesized from either an aldehyde(which proceeds via a nitrile), a nitrile, or a Suzuki cross-couplingreaction. These precursors possess four tert-butyldimethylsiyl protectedhydroxy groups (depicted as “OTBS” groups in FIGS. 6A, 6B, 7, and 8)which are then reacted with specific reagents that will cause anucleophilic substitution to occur at each of the four imines on thecentral tetrazine ring. This results in a tetra-quaternized tetraziniummonomer. Selecting the reagents and conditions of the nucleophilicsubstitutions results in different counter cations which affect thesolubility of the monomer and any resulting polymers synthesized fromthe monomers. The tetrazinium monomer is polymerized with donor(electron rich) molecules by cross-coupling reactions.

Referring to FIGS. 6A and 6B, a diagram 600 illustrates an example of aprocess of forming the tetrazine monomer precursor depicted in FIGS. 1Aand 1B. FIG. 6A is a first chemical reaction diagram that depicts anexample of a process of forming a TBS-protected molecule, and FIG. 6A isa second chemical reaction diagram that depicts an example of a processof utilizing the TBS-protected molecule to form the tetrazine monomerprecursor depicted in FIGS. 1A and 1B. As described further herein withrespect to FIGS. 1A and 1B, the tetrazine monomer precursor may beutilized to form either the first quaternized tetrazine monomer(depicted in FIG. 1A) or the second quaternized tetrazine monomer(depicted in FIG. 1B).

PROPHETIC EXAMPLE Synthesis of TBS-Protected Molecule

[First Chemical reaction depicted in FIG. 6A, identified as step 1]:5-bromo-2-iodo-1,3-dimethylbenzene (1.0 equiv.), N-bromosuccinimide(>2.0 equiv.) was added to a stirred solution of AIBN (0.02 mol%) inbenzene, DCM, Chloroform, or carbon tetrachloride at room temperature.The reaction mixture was heated to reflux and stirred for 5 hours, atwhich time the product had precipitated. The reaction mixture wasallowed to cool to room temperature, and the product was filtered andwashed with cold dichloromethane (5×100 mL). The white solid was driedin vacuo. The resulting white solid was used in the subsequent reactionwithout further purification.

[First Chemical reaction depicted in FIG. 6A, identified as step 2]: Asolution of the product from the previous step (1.0 equiv.) andtriphenylphosphine (2.5 equiv.) in dimethylformamide was heated atreflux for 18 hours. The solvent was removed, and the residue wasdissolved in tetrahydrofuran, and an excess of paraformaldehyde wasadded. Potassium tert-butoxide (3.0 equiv.) in tetrahydrofuran was thentransferred in the reaction vessel. The solvent was evaporated, and theresidue was purified on a silica gel column with hexane as the eluent.Removal of solvent and recrystallization from absolute ethanol may alsobe used.

[Second Chemical reaction depicted in FIG. 6A, identified as steps 1 and2]: 9-BBN (0.5 M in THF, 2.1 equiv.) was added dropwise over 30 min to astirred and cooled (0° C.) solution of 1-iodo-4-bromo-2,6-divinylbenzene(8.68 g, 1.0 equiv.) in THF (125 mL). The ice bath was removed, andstirring was continued for 10 hours. The mixture was cooled to 0° C. andquenched by dropwise addition of MeOH. Aqueous NaOH (2 M, >1.5 equiv.)and 30% H₂O₂ (>10.0 equiv.) were poured into the stirred mixture.Stirring was continued for 2 h, and the mixture was extracted with Et₂O.The combined organic extracts were washed with brine, dried (Na₂SO₄),and the solvent was evaporated. The crude product was purified throughcolumn chromatography (silica gel, hexane/EtOAc=3/1).

[Second Chemical reaction depicted in FIG. 6A, identified as step 3]:The tetrahydroxy product from the previous step (1.0 equiv.) and acatalytic amount of imidazole were dissolved in an organic solvent suchas DCM. Tert-butyldimethylsilyl chloride (>2.0 equiv.) was added in oneportion to the reaction and the mixture was stirred at room temperatureuntil completion. The reaction was washed with water, brine, and theorganic layer was dried over MgSO₄. The solvents were removed in vacuoand the crude product may be purified via recrystallization, columnchromatography, or by techniques known to those skilled in the arts.

PROPHETIC EXAMPLE Synthesis of Tetrazine Monomer Precursor

[First Chemical reaction depicted in FIG. 6B, identified as steps 1-3]:A solution of the compound from the previous (1.0 equiv.) in dry THF maybe sparged with Argon. The solution may be cooled to −15° C., i-PrMgCl(2M in THF, 1.05 equiv.) may be added and the reaction may be stirredfor 2 hours at −15° C. Then, dry DMF (14.24 mmol, 1.1 mL) may be addedand the reaction may be allowed to warm over 1 hour. The reaction mat bequenched with aqueous 1M HCl and extracted with diethyl ether. Theorganic layer may be washed with brine, dried over anhydrous sodiumsulfate, filtered, and concentrated. The resulting crude may be purifiedby flash chromatography on silica gel.

[Second Chemical reaction depicted in FIG. 6B, identified as steps 1 and2]: A mixture solution of the aldehyde from the previous step (1.0equiv.) and hydroxylamine hydrochloride salt (1.5 equiv.) inpyridine/ethanol (1:1 v/v) was stirred at 80° C. overnight. Then thesolvent was removed in vacuo. The residue was dissolved in chloroform(100 mL), and the solution was washed with distilled water (2×50 mL) anddried over anhydrous magnesium sulfate. The solvent was removed invacuo, and the viscous residue was dissolved in acetic anhydridecontaining catalytic potassium acetate and then refluxed for 3 hours.The mixture was poured into distilled water and extracted with hexanes(3×). The organic phase was washed with 5% aqueous sodium hydroxidesolution and then water, dried over anhydrous magnesium sulfate beforethe solvent was removed in vacuo. The residue was purified by silica-gelcolumn chromatography.

[Second Chemical reaction depicted in FIG. 6B, identified as step 3]: Toa mixture of the nitrile from the previous step (1.0 equiv.) and sulphur(0.7 equiv.) in anhydrous ethanol was slowly added fresh hydrazinemonohydrate (1.5 equiv.) at room temperature. The solution turned intoyellow and large amount of gas evolved. The solution was heated up toreflux and stirred for 2 hours and was cooled down to room temperature.Crystals were allowed to form in solution, were collected by filtrationand rinsed with cold ethanol before dried under vacuum. To a chloroformsolution (50 mL) of the obtained solid, isoamyl nitrite (5.58 g, 2.0equiv.) was added and the solution was stirred at room temperatureovernight. The solvent was removed and the resulting red solid waswashed with methanol twice before purified by silica-gel columnchromatography.

Thus, FIGS. 6A and 6B illustrate an example of a process of forming atetrazine monomer precursor that may be utilized in the synthesis of thequaternized tetrazine-based D-A copolymers of the present disclosure.

Referring to FIG. 7, a chemical reaction diagram 700 illustrates analternative process of forming the tetrazine monomer precursor depictedin FIGS. 1A and 1B.

PROPHETIC EXAMPLE Synthesis of Tetrazine Monomer Precursor

[First chemical reaction depicted in FIG. 7]: The starting material (1.0equiv.) was dissolved in of DMF and treated with 9.92 g (>1.0 equiv.) ofCuCN. The system may be flushed with nitrogen, after which the mixturewarmed to 100° C. and stirred for 18 hours. The mixture was allowed tocool to room temperature, and any precipitates were removed viafiltration and washed with ethyl acetate. The combined organics werediluted with water and then extracted with ethyl acetate (2×). Thecombined layers were dried over sodium sulfate, filtered, and evaporatedto dryness. Additional purification steps may be performed such asrecrystallization or column chromatography (among other alternatives).

[First chemical reaction depicted in FIG. 7]: Similar reactionconditions utilized as described above with respect to step 3 of thesecond chemical reaction of FIG. 6B may be used to form the tetrazinemonomer precursor.

Referring to FIG. 8, a chemical reaction diagram 800 illustrates analternative process of forming the tetrazine monomer precursor depictedin FIGS. 1A and 1B.

PROPHETIC EXAMPLE Synthesis of Tetrazine Monomer

To a solution of dibromo or dichlorotetrazine (1.0 equiv.) in DMF wasadded potassium acetate (3.0 equiv.), bis(pinacolato)diboron (>1.5equiv.), and Pd(dppf)Cl₂ (5 mol%). The reaction mixture was stirred at110° C. until completion. Brine (5 mL) was added, followed by EtOAc (10mL). The layers were separated, and the organic layer was dried,filtered, and concentrated in vacuo.

PROPHETIC EXAMPLE Synthesis of Tetrazine Monomer Precursor

A reaction vessel may be charged with the phenyliodide (>2.0 equiv.),and the diboronic ester (1.0 equiv.), palladium catalyst (1-5 mol %)such as palladium acetate(II) or palladium tetrakis(triphenylphosphine),and a ligand such as tri(o-tolyl)phospine (3-10 mol %). The atmosphereof the reaction vessel may be displaced with an inert gas such asnitrogen or argon. A degassed solvent mixture such dimethyl ether andaqueous solution of an alkaline base such as cesium carbonate (>2equiv., 2.0 M) may be added to the reaction vessel. A phase transferagent such as aliquat 336 may be added to the reaction mixture and thereaction mixture may be stirred at reflux for an extended period of timeuntil the reaction is complete. The mixture may be allowed to cool toroom temperature, and any precipitates may be removed via filtration andwashed with ethyl acetate. The combined organics may be diluted withwater and then extracted with ethyl acetate (2×). The combined layersmay be dried over sodium sulfate, filtered, and evaporated to dryness.Additional purification steps may be performed such as recrystallizationor column chromatography.

Referring to FIG. 9, a flow diagram illustrates an exemplary process 900of forming a quaternized tetrazine-based D-A copolymer, according to aparticular embodiment. In the particular embodiment illustrated in FIG.9, operations associated with forming a quaternized tetrazine monomermaterial are identified as operations 902-904, while operationsassociated with forming a quaternized tetrazine-based D-A copolymer areidentified as operation 906. It will be appreciated that the operationsshown in FIG. 9 are for illustrative purposes only and that the chemicalreactions may be performed in alternative orders, at alternative times,by a single entity or by multiple entities, or a combination thereof. Asan example, one entity may form the tetrazine monomer precursormaterial, and another entity may form the quaternized tetrazine monomermaterial, while another entity may form the quaternized tetrazine-basedD-A copolymer. Further, alternative or additional entities may performoperations associated with forming the donor material(s) forpolymerization with the quaternized tetrazine monomer material.

The process 900 includes forming a tetrazine monomer precursor material,at 902. For example, the tetrazine monomer precursor material depictedin FIGS. 1A and 1B may be formed according to the process describedherein with respect to FIGS. 6A and 6B. As another example, thetetrazine monomer precursor material depicted in FIGS. 1A and 1B may beformed according to the process described herein with respect to FIG. 7.As a further example, the tetrazine monomer precursor material depictedin FIGS. 1A and 1B may be formed according to the process describedherein with respect to FIG. 8.

The process 900 includes forming a quaternized tetrazine monomermaterial from the tetrazine monomer precursor material, at 904. Forexample, referring to FIG. 1A, the tetrazine monomer precursor materialmay be utilized to form the first quaternized tetrazine monomermaterial. As another example, referring to FIG. 1B, the tetrazinemonomer precursor material may be utilized to form the secondquaternized tetrazine monomer material.

The process 900 includes polymerizing the quaternized tetrazine monomermaterial and a donor material to form a quaternized tetrazine-based D-Acopolymer, at 906. For example, referring to FIG. 2, the firstquaternized tetrazine monomer material (depicted in FIG. 1A) may bepolymerized with one or more donor (electron rich) molecules to form thefirst quaternized tetrazine-based D-A copolymer. As another example,referring to FIG. 3, the second quaternized tetrazine monomer material(depicted in FIG. 1B) may be polymerized with one or more donor(electron rich) molecules to form the second quaternized tetrazine-basedD-A copolymer.

Thus, FIG. 9 illustrates an example of a process of forming aquaternized tetrazine-based D-A copolymer. In some cases, as describedfurther herein with respect to FIG. 10, the quaternized tetrazine-basedD-A copolymer(s) of the present disclosure may be utilized to form aportion of an OPV device.

Referring to FIG. 10, a flow diagram illustrates an exemplary process1000 of forming an active layer of an OPV device from a blend thatincludes the quaternized tetrazine-based D-A copolymer(s) of the presentdisclosure, according to one embodiment. While FIG. 10 depicts anexample in which the quaternized tetrazine-based D-A copolymer(s) of thepresent disclosure are used as a component of an OPV device, it will beappreciated that the quaternized tetrazine-based D-A copolymer(s) of thepresent disclosure may be used in other contexts, such as organicbatteries or organic sensors (among other alternatives).

In the particular embodiment illustrated in FIG. 10, operationsassociated with formation of a blend of materials that includes thequaternized tetrazine-based D-A copolymer(s) of the present disclosureare identified as 1002, while operations associated with formation of anactive layer of an OPV device from the blend are identified as 1004. Itwill be appreciated that the operations shown in FIG. 10 are forillustrative purposes only and that the operations may be performed inalternative orders, at alternative times, by a single entity or bymultiple entities, or a combination thereof. As an example, one entitymay produce the quaternized tetrazine-based D-A copolymer(s), anotherentity (or entities) may produce the other material(s) for the blend,while another entity may mix the materials to form the blend. Further,alternative or additional entities may perform operations associatedwith forming the active layer of the OPV device from the blend.

The process 1000 includes forming a blend that includes a quaternizedtetrazine-based D-A copolymer (or multiple quaternized tetrazine-basedD-A copolymers) and one or more other materials, at 1002. The process1000 also includes forming an active layer of an OPV device from theblend, at 1004. For example, the first quaternized tetrazine-based D-Acopolymer depicted in FIGS. 2 and 4B and/or the second quaternizedtetrazine-based D-A copolymer depicted in FIGS. 3 and 5B may be mixedwith one or more other materials to form a blend. As an example, thequaternized tetrazine-based D-A copolymer(s) of the present disclosuremay represent a p-type material. In this case, the quaternizedtetrazine-based D-A copolymer(s) may be mixed with one or more n-typematerials that are suitable for use in an active layer of an OPV device.As described further herein, the quaternized tetrazine-based D-Acopolymers of the present disclosure have desirable solubilitycharacteristics, allowing for processing by common polar solvents, suchas chloroform, chlorobenzenes, dimethylformamide, toluene, and THF.Further, the high ionic content of the quaternized tetrazine-based D-Acopolymers of the present disclosure may allow for processing by polarprotic solvents such as water, ethanol, and isopropanol.

It will be understood from the foregoing description that modificationsand changes may be made in various embodiments of the present inventionwithout departing from its true spirit. The descriptions in thisspecification are for purposes of illustration only and are not to beconstrued in a limiting sense. The scope of the present invention islimited only by the language of the following claims.

What is claimed is:
 1. An organic photovoltaic device comprising anactive layer that includes a quaternized tetrazine-based donor acceptor(D-A) copolymer.
 2. The organic photovoltaic device of claim 1, whereinthe active layer further includes an n-type material.
 3. The organicphotovoltaic device of claim 1, wherein the active layer is formed froma solution that includes the quaternized tetrazine-based D-A copolymerand a polar protic solvent.
 4. The organic photovoltaic device of claim3, wherein the polar protic solvent includes water, ethanol,isopropanol, or a combination thereof.
 5. The organic photovoltaicdevice of claim 1, wherein the active layer is formed from a solutionthat includes the quaternized tetrazine-based D-A copolymer and a polarorganic solvent.
 6. The organic photovoltaic device of claim 5, whereinthe polar organic solvent includes chloroform, tetrahydrofuran (THF),dimethylformamide (DMF), chlorobenzene, dichlorobenzene, or acombination thereof.
 7. The organic photovoltaic device of claim 1,wherein the quaternized tetrazine-based donor acceptor (D-A) copolymercomprises iminium cations.
 8. The organic photovoltaic device of claim1, wherein the quaternized tetrazine-based D-A copolymer includes fourchloride anions per polymeric repeat unit.
 9. The organic photovoltaicdevice of claim 8, wherein the quaternized tetrazine-based D-A copolymeris soluble in water.
 10. The organic photovoltaic device of claim 1,wherein the quaternized tetrazine-based D-A copolymer includes alkylsulfite anions per polymeric repeat unit.
 11. The organic photovoltaicdevice of claim 10, wherein the quaternized tetrazine-based D-Acopolymer is soluble in a polar organic solvent.
 12. The organicphotovoltaic device of claim 11, wherein the polar organic solventincludes chloroform, THF, DMF, chlorobenzene, dichlorobenzene, or acombination thereof.